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Bias-free solar NH3 production by perovskite-based photocathode coupled to valorization of glycerol

Nature Catalysis (2024)Cite this article

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Abstract

Photoelectrochemical production of ammonia (NH3) is potentially eco-friendly but suffers from a low solar-to-ammonia productivity (SAP) and requires a high additional bias for the overall NH3 production from nitrate reduction and water oxidation. Here we applied a high-performance triple-cation lead halide (Cs0.05(FA0.83MA0.17)0.95Pb(Br0.17I0.83)3) perovskite photocathode with integrated electrocatalyst to achieve high SAP and coupled glycerol oxidation instead of water oxidation for bias-free NH3 production. Stable, selective NH3 production and glycerol oxidation were achieved by respectively loading Ru and Pt electrocatalysts on conductive and stable titanate nanosheet supports, instead of corrodible carbon-based supports. Our photoelectrochemical NH3 production system coupled to glycerol oxidation demonstrated a photocurrent density of 21.2 ± 0.7 mA cm−2 and SAP of 1,744.9 ± 20.6 µgNH3 cm−2 h−1 with 99.5 ± 0.8% Faradaic efficiency without applying any additional bias. Simultaneously, glycerol was selectively oxidized to glyceric acid as a major value-added product.

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Fig. 1: Schematic of the PEC cell used for NH3 production.
Fig. 2: Characterization and performance of Ru@TiNS electrocatalyst for NH3 production.
Fig. 3: PEC performance of perovskite photocathode for NH3 production.
Fig. 4: Physiochemical and morphological characterization of prepared electrocatalysts.
Fig. 5: Unassisted NH3 production with simultaneous glycerol valorization.

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The experimental data in the main text or Supplementary Information during the current study are included in the paper and its Supplementary Information. Source data are provided with this paper.

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Acknowledgements

The National Research Foundation (NRF; RS-2023-00222006 and 2023R1A2C3002881 to J.S.-Y.; 2019M1A2A2065612, 2021R1C1C1012258, 2019H1D3A1A01103006, 2016R1A5A1012966 and 2022H1D3A3A01081140 to J.-W.J.), as well as the Research Fund (1.230040.01 to J.-W.J.) of the UNIST, sponsored this study (Ulsan National Institute of Science and Technology). J.-W.J. also acknowledges the Alchemist Project funded by the Ministry of Trade, Industry and Energy thorough the Korean Evaluation Institute of Industrial Technology (1415184376 (20019321)). T.F.J. was supported as part of the Cleantech FWP 100898 funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES) for ATR-SEIRAS studies. J.M. acknowledges a graduate fellowship through the National Science Foundation Graduate Research Fellowship under grant no. DGE-1656518. Experiments at PLS-II 6D UNIST-PAL beamline were supported in part by MSIT, POSTECH and UNIST Central Research Facilities.

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Author notes

  1. These authors contributed equally: Ahmad Tayyebi, Rashmi Mehrotra, Muhibullah Al Mubarok, Jieun Kim.

Authors and Affiliations

  1. School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology, Ulsan, Republic of Korea

    Ahmad Tayyebi, Rashmi Mehrotra, Muhibullah Al Mubarok, Jieun Kim, Dongrak Oh, Sung-Yeon Jang & Ji-Wook Jang

  2. Department of Chemistry, Ulsan National Institute of Science and Technology, Ulsan, Republic of Korea

    Mohammad Zafari & Geunsik Lee

  3. Advanced Industrial Chemistry Research Center, Advanced Convergent Chemistry Division, Korea Research Institute of Chemical Technology, Ulsan, Republic of Korea

    Meysam Tayebi

  4. SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University, Stanford, CA, USA

    Dongrak Oh, Jesse E. Matthews, Sang-Won Lee & Thomas F. Jaramillo

  5. SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, Menlo Park, CA, USA

    Dongrak Oh, Jesse E. Matthews, Sang-Won Lee & Thomas F. Jaramillo

  6. Graduate School of Semiconductor Materials and Devices Engineering, Ulsan National Institute of Science and Technology, Ulsan, Republic of Korea

    Seong-hun Lee & Tae Joo Shin

  7. Graduate School of Carbon Neutrality, Ulsan National Institute of Science and Technology, Ulsan, Republic of Korea

    Sung-Yeon Jang & Ji-Wook Jang

  8. Emergent Hydrogen Technology R&D Centre, Ulsan National Institute of Science and Technology, Ulsan, Republic of Korea

    Ji-Wook Jang

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  1. Ahmad Tayyebi
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Contributions

A.T. and J.-W.J. conceived and proposed this work. T.F.J., S.-Y.J. and J.-W.J. directed the project. A.T., R.M., M.A.M. and J.K. designed and performed the experiments. A.T. synthesized and characterized Ru@TiNS, Pt@TiNS and Ru@rGO. J.K. and A.T. measured the catalytic performance for NITRR, and GOR with quantification of products. M.A.M. prepared and characterized the perovskite. R.M. integrated perovskite with Ru@TiNS and conducted the PEC experiments. A.T. and R.M. designed and performed the bias-free experiments. M.Z. and G.L. performed the DFT calculations and analysed them. M.T. analysed and deconvoluted the XPS results. D.O. helped with the UV–Vis and HPLC measurements. D.O., J.E.M., S.-W.L. and T.F.J. measured and analysed the in situ IR spectra. S.-h.L. and T.J.S. conducted XANES and EXAFS experiments and analysed them. A.T., R.M., M.A.M., J.K., T.F.J., J.S.-Y. and J.-W.J. co-wrote the manuscript. All authors read and commented on the manuscript.

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Correspondence to Thomas F. Jaramillo, Sung-Yeon Jang or Ji-Wook Jang.

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Nature Catalysis thanks Jungang Hou and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Information

Supplementary Figs. 1–45, Tables 1–7, Notes 1–5 and references.

Supplementary Data 1

Source data for Supplementary Figs. 1–45 and Tables 1–7.

Supplementary Code 2

Source data for supplementary DFT structure (zip file of Supplementary Figs. 19a–d and 20a,b).

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Source Data Fig. 3

Source data and statistical source data for Fig. 3e.

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Source data.

Source Data Fig. 5

Source data and statistical source data for Fig. 5e,f,h.

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Tayyebi, A., Mehrotra, R., Mubarok, M.A. et al. Bias-free solar NH3 production by perovskite-based photocathode coupled to valorization of glycerol. Nat Catal (2024). https://doi.org/10.1038/s41929-024-01133-4

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